JPH07116130B2 - Acrylic acid derivative, method for producing the same, and fungicide, insecticide or plant growth regulator composition containing the same - Google Patents

Abstract

Compounds of formula: <CHEM> and stereoisomers thereof, wherein R<1> and R<2>, which are the same or different, are optionally substituted alkyl; W, X, Y and Z, which are the same or different, are hydrogen, halogen, hydroxy, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted aralkyl, optionally substituted aryloxyalkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, optionally substituted amino, optionally substituted arylazo, optionally substituted heteroarylalkyl, optionally substituted heteroaryloxyalkyl, optionally substituted acylamino, nitro, cyano, -OR<3>, -SR<3>, -CO2R<4>, -CONR<5>R<6>, -COR<7>, -CR<8>=NR<9>, -N=CR<1><0>R<1><1>, -SOR<1><2> or SO2R<1><3>, or any two of W, X, Y, and Z, in adjacent positions on the phenyl ring, optionally join to form an optionally substituted fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; R<3> is optionally substituted alkyl, or cycloalkyl optionally containing a hetero atom in the cycloalkyl ring, optionally substituted alkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted acyl, or optionally substituted heteroaryl; R<4>, R<5>, R<6>, R<7>, R<8>, R<1><0> and R<1><1>, which are the same or different, are hydrogen or optionally substituted alkyl, optionally substituted cycloalkyl, cycloalkylalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted aralkyl; and R<9>, R<1><2> and R<1><3> are optionally substituted aryl or optionally substituted heteroaryl. The compounds are useful as fungicides and insecticides and regulating plant growth.

Description

The present invention relates to an acrylic acid derivative useful in agriculture and horticulture (particularly as a fungicide, and also as a plant growth regulator and insecticide), a method for producing the same, and an agricultural chemical containing the same (particularly a fungicide). ) Relates to a composition.

According to the invention, the general formula (I): (In the formula, R ¹ and R ² are the same or different,
And represents an optionally substituted alkyl group (especially a methyl group); W, X, Y and Z are the same or different and hydrogen, halogen (fluorine, chlorine, bromine or iodine) , A hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkylalkyl group, an optionally substituted aralkyl group, an optionally substituted aryloxyalkyl group, An optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted arylazo group, an optionally substituted heteroarylalkyl group, A heteroaryloxyalkyl group substituted by, optionally substituted acylamido Group, a nitro group, a cyano group, -O
_{^{R 3, -SR 3, -CO 2}} R 4, -CONR 5 R 6, -COR 7, -CR 8 = N
^{R 9, -N = CR 10 R} 11, or represents -SOR ¹² or -SO ₂ R ^13,
Or any two W, X, Y and Z in adjacent positions on the phenyl ring are optionally linked and are aromatic or aliphatic rings and optionally one or more A heteroatom-containing, optionally substituted fused ring; R ³ is an optionally substituted alkyl group or a cycloalkyl group optionally containing a heteroatom in the cycloalkyl ring, optionally substituted Represents an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted acyl group or an optionally substituted heteroaryl group; R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are the same or different and are hydrogen or an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted A substituted cycloalkylalkyl group,
An optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group,
Acrylic acid represented by an optionally substituted heteroaryl group or an optionally substituted aralkyl group; and R ⁹ , R ¹² and R ¹³ represent an optionally substituted aryl group or a substituted heteroaryl group) Derivatives and stereoisomers thereof are provided.

The compounds of the present invention contain at least one carbon-carbon double bond and are often obtained in the form of a mixture of geometric isomers. However, these mixtures can be resolved into the individual isomers, and therefore the present invention consists of such isomers, and those consisting essentially of ( Z ) -isomers and substantially ( E ) -isomers. Also included are mixtures of all of these isomers, including

The individual isomers resulting from the asymmetrically substituted double bond of the acrylate group are distinguished below by the commonly used terms " E " and " Z ". These terms are described in detail in the literature “Cahn-Ingold-Pr.
elog System "[eg J. Marc
h, "Advanced Organic Chemistry", 3rd edition, Wiley-Int
erscience, page 109 et seq.].

In the following, the formula: By using two geometric isomers about the acrylate double bond: Shows a dividable mixture consisting of

In the compound of general formula (I), an alkyl group and an alcohol
The alkyl part of the xy group must be in the form of a straight chain or a branched chain.
And preferably 1 to 6, more preferably 1 to
It contains 4 carbon atoms. Examples are methyl, ethyl,
Propyl (n-Andiso-Propyl) and butyl groups (n
-,sec-Andtert-Butyl). In some cases
Substituents which may be present in the kill include hydroxyl, halo
Gen (especially chlorine or fluorine) and alkoxycarbonyl groups
Is mentioned. As an optionally substituted alkyl group
Of particular interest is the trifluoromethyl group.

Both optionally substituted alkyl groups R ¹ and R ² are preferably methyl groups. If it has a substituent, the preferred substituent is fluorine, which may be present one or more times.

Examples of the cycloalkyl group (which is preferably a C _3-6 cycloalkyl group) include a cyclohexyl group, and a cycloalkylalkyl group (which is a C _3-6 cycloalkyl (C _1-4 ) alkyl group Is preferred)
Includes a cyclopropylethyl group. An example of a cycloalkyl group containing a heteroatom is a tetrahydroplanyl group.

As the aralkyl group, a phenylalkyl group (especially,
Benzyl, phenylethyl, phenylpropyl, phenylbutyl or phenylhexyl groups); the alkyl group part of the phenylalkyl group may have other substituents such as a hydroxyl group and the aryl group part may, for example, be any of the substituents given below. May be substituted by one or more; halogen, hydroxyl, C _1-4 alkyl (especially methyl and ethyl), C _1-4 alkoxy (especially methoxy), halo (C _1-4 ) alkyl (especially trifluoromethyl) , Halo (C _1-4 ) alkoxy (especially tolfluoromethoxy), C _1-4 alkylthio (especially methylthio), C _1-4 alkoxy (C _1-4 ) alkyl, C _3-6 cycloalkyl, C _{3- 6}
Cycloalkyl (C _1-4 ) alkyl, aryl (especially phenyl), aryloxy (especially phenyloxy), aryl (C _1-4 ) alkyl (especially benzyl, phenylethyl and phenyl n-propyl), aryl (C _1-4 ). Alkoxy (especially benzyloxy), aryloxy (C _1-4 ).
Alkyl (especially phenyloxymethyl), acyloxy (especially acetyloxy and benzyloxy), cyano,
Thiocyanato, nitro, -NR'R ", -NHCOR ', -NHC
ONR'R ", -CONR'R", -COOR ", -OSO ₂ R ', -SO
₂ R ', -COR', -CR '= NR "or -N = CR'R" group (R' and R "in the above formula are hydrogen, C _1-4 alkyl, C _1-4 alkoxy, respectively. , C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, phenyl or benzyl group, which phenyl and benzyl groups may be halogen, C _1-4 alkyl. Or is substituted with a C _1-4 alkoxy group).

The aryloxyalkyl group includes, in particular, a phenoxyalkyl group (particularly a phenoxymethyl or phenoxyethyl group), and the alkyl group moiety may have other substituents such as a hydroxyl group, and
The aryl group moiety may have the same substituents as the aryl group moiety in the aralkyl group.

The alkenyl and alkynyl groups preferably contain 2 to 6, more preferably 2 to 4 carbon atoms in the form of straight or branched chains. Examples of alkenyl groups are ethenyl, propenyl and butenyl groups. Substituents that may optionally be present in the alkenyl group (especially the ethenyl group) include aromatic and heteroaromatic groups (eg phenyl, furyl, thienyl or pyridyl groups) and these groups are
As such, it may carry substituents, especially halogens (especially chlorine or fluorine), such as those carried by the aryl moieties in the aralkyl groups. Further, the terminal carbon atoms of the alkenyl group may form part of a 5- or 6-membered cycloalkyl group. Alkynyl groups include ethynyl groups, which are optionally substituted, for example by aryl groups, and which aryl groups themselves may have the same substituents as the aryl group moieties in said aralkyl groups.

The aryl group is preferably a phenyl group; the heteroaryl group is pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,3-, 1,2,4-
And heteroaromatics such as 1,3,5-triazinyl, 1,2,4,5-tetrazinyl, thienyl, quinolinyl, isoquinolinyl, quinoxalinyl and benzothiophenenyl groups.
roaromatic) groups; these groups may have the same substituents as the aryl moiety in the aralkyl group.

Examples of optionally substituted amino, acylamino and acyl groups include the groups —NR′R ″, —NHCOR ′ and —COR ′, where R ′ and R ″ have the meanings given above.
Examples of the acyl group include formyl, acetyl and benzoyl groups, and examples of the acylamino group include benzoylamino and furoylamino optionally substituted with, for example, an N- (C _1-4 ) alkyl group (especially N-methyl group). Groups.

The arylazo group is, for example, a phenylazo group in which the aryl group moiety is substituted with the same substituents as the aryl group moiety in the aralkyl group, particularly, an alkynyl, alkoxy (especially methoxy) or dialkylamino group (especially dimethylamino). is there. Heteroarylalkyl (hete
roarylalkyl) and heteroaryloxyalkyl (het)
The term eroaryloxyalkyl) group is an alkyl group and is a heteroaromatic substituent including pyridinyl, pyrimidinyl, thienyl, furyl and pyrrolyl groups (in the case of heteroaryloxyalkyl groups, linked by an oxygen atom). ) Is supported (preferably a C _1-4 alkyl group, particularly an ethyl group in the case of a heteroarylalkyl group and a methyl group in the case of a heteroaryloxyalkyl group). The heteroaromatic group moiety is
In some cases, a substituent similar to the aryl moiety in the aralkyl group, particularly trifluoromethyl, halogen (especially fluorine, chlorine or bromine), nitro, C _1-4 alkyl, C _1-4
It is substituted by alkoxy, trifluoromethoxy and amino groups.

Whenever the term optionally substituted aryl or heteroaryl group moiety or optionally substituted fused ring is used, the substituent group may be present in the aryl group moiety in said aralkyl group. Means a substituent.

According to one aspect of the invention, the general formula (Ia): [Wherein W, X, Y and Z are the same or different, and are substituted by hydrogen, halogen (especially fluorine or chlorine), and optionally a hydroxyl group or a C _1-4 alkoxycarbonyl group. C _1-4 alkyl group, trifluoromethyl group, phenyl (C _1-4 ) alkyl group, C _2-4 alkenyl group or itself, optionally substituted with, for example, halogen (especially fluorine or chlorine) Aromatic or heteroaromatic groups in which the terminal carbon atoms of the group or heteroaromatic or alkenyl groups form part of a 5- or 6-membered cycloalkyl group (eg phenyl, furyl, thienyl or pyridinyl groups) ) to O connexion substituted by are C _2-4 alkenyl group (especially ethenyl, propenyl or butenyl group), optionally substituted alkynyl groups (e.g., phenylalanine ethynyl group), if Ri substituted aryl group (especially phenyl group), an amino group substituted by an aryl group or a C _1-4 alkyl group (e.g. phenyl or methyl group), optionally for example C _1-4 alkyl group, C _1-4 alkoxy Arylazo groups (especially phenylazo groups) substituted by groups (especially methoxy groups) or N , N -di (C _1-4 ) alkylamino groups (especially N , N -dimethylamino groups), optionally eg (N-methyl An acylamino group (especially benzoylamino or furoylamino group) substituted by an N-alkyl group, a nitro group, —SR ³ or —OR ³ [wherein R ³ is an optionally substituted alkyl group, and optionally Substituted aryl group (especially phenyl group), optionally substituted heteroaryl group, optionally substituted aralkyl group or acyl group (eg benzoyl group) Represents], -SOR ¹² or -SO ₂ R ¹³ wherein, R ¹² and R ^13, an aryl group (e.g. phenyl group), or represents -CO ₂ R ^4, R
⁴ is an optionally substituted alkyl group (especially C _1-4 alkyl group such as tert-butyl group), aryl group (especially phenyl group), C _3-6 cycloalkyl group (especially cyclohexyl group), C _3-6 A cycloalkyl (C _1-4 ) alkyl group or an aryl (C _1-4 ) alkyl group] or —COR ⁷ [in the formula, R ⁷
Represents an optionally substituted alkyl group (especially a methyl group) or an optionally substituted aryl group (eg a phenyl or methoxyphenyl group), or W at an adjacent position on the phenyl ring. , X, Y, and Z combine to form a condensed ring (for example, a condensed benzene, naphthalene, or benzofuran ring)]
And a stereoisomer thereof.

It is preferred that at least one of W, X, Y and Z be a substituent other than hydrogen and that this substituent be in the ortho position on the phenyl ring with respect to the acrylate group.

Further, when two or more of W, X, Y and Z are substituents other than hydrogen, one or more of the additional substituents is a single atom or fluorine, chlorine, bromine Sterically (ster, such as hydroxyl, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, nitro, cyano, amino, methylamino, dimethylamino, carboxy, acetyl or methoxycarbonyl groups.
It is preferably a radically small group.

According to yet another aspect of the present invention, the general formula (Ib): [Wherein R is hydrogen, a C _1-4 alkylthio group, a C _1-4 alkyl group optionally substituted by a phenylthio group or a phenyl group, a C _3-6 cycloalkyl group (particularly a cyclohexyl group), a tetrahydropyranyl group A C _2-4 alkenyl group (particularly an ethenyl, propenyl or phenylethenyl group), a phenyl group or a halogen (fluorine, chlorine, bromine or iodine),
Hydroxyl group, C _1-4 alkyl group, C _1-4 alkoxy group (especially methoxy group), tolufluoromethoxy group, phenoxy group, nitro group, amino group, aryl (C _1-4 ) alkyl group (especially benzyl group) ), A phenyl group, a carboxyl group, a carboxylic acid ester group (particularly a methyl ester group),
A phenyl group, naphthyl group, pyridinyl group or pyrimidinyl group [pyridinyl and pyrimidinyl moiety substituted by one or more of a cyano group, a C _1-4 alkylcarbonylamino group (particularly a methylcarbonylamino group) or a methylenedioxy group Optionally halogen (especially fluorine, chlorine or bromine), trifluoromethyl group, nitro group, C _1-4 alkyl group (especially methyl group), C _1-4 alkoxy group (especially methoxy group), trifluoromethoxy group Or substituted by an amino group], Y and Z are the same or different, and hydrogen, halogen (especially fluorine or chlorine), C _1-4 alkyl group (especially methyl group) , C _1-4 alkoxy (especially methoxy), C _1-4 alkylthio group (especially methylthio), trifluoromethyl group, nitro group, or N, N - di C _1-4) - alkylamino group (particularly N, N-dimethylamino group) or represents, or Y and Z of the compound represented by forming a connexion methylenedioxy group together] is provided .

According to yet another aspect of the present invention, a compound of general formula (Ic) (Wherein Y and Z have the same meanings as defined for the compound of the general formula (Ib), provided that R may further represent a thienyl group, a furyl group or a pyrrolyl group) Provided.

According to yet another aspect of the present invention, the general formula (Id) There is provided a compound represented by the formula (wherein R, Y and Z have the same meanings as defined for the general formula (Ic)).

Examples of compounds of the invention are shown in Tables I and II below.

The present invention has the following formula: (Wherein R has any of the definitions for R given in Table II, and Y and Z are single atoms or hydrogen (provided that neither is hydrogen), or fluorine, chlorine, bromine. ,
A sterically small group such as a hydroxyl, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, nitro, cyano, amino, methylamino, dimethylamino, carboxy, acetyl or methoxycarbonyl group; The format is II
Compounds shown in Table I).
The acrylate group may in each case have an ( E ) or ( Z ) type geometrical isomeric structure.

Specific examples of compounds of the type shown in Table III are given below: The invention further has the formula: (Wherein R has any of the definitions for R in Table II). Included in the above compounds are compounds No. 50, 96 and 97 of Table I.

The invention further has the formula: (Wherein R has any of the definitions for R in Table II). Included among the above compounds are compounds No. 57-59, 71 and 83 of Table I.

The present invention further provides the following groups: Are excited by compounds bearing the substituents Y and Z having the same meaning as defined for the compounds in Table II, including combinations of the meanings defined in Table III.

Compounds of general formula (I) may be prepared from a variety of compounds as shown in Scheme I. This compound exists as geometric isomers, which can be separated by chromatography, distillation or fractional crystallization. In Process Diagram I, W, X,
Y, Z, R ¹ and R ² have the meanings given above, R ¹⁴ is an alkyl group and R ¹⁵ is an alkyl group or an optionally substituted aryl group.

The compound of the present invention having the general formula (I) can be produced by the following method. Each reaction is carried out in a convenient solvent.

Arufua of (i) Formula (II) - ketoester of _{^{formula: Ph 3 P + - - CHSR}} 2 phosphorane or formula: Me ₃ SiCH (Li) method is treated with lithiated kind of SR ² (lithio-species) [e.g. DJPeterson , J.Org.Chem ., 33 , 780 (1
968);.. FACarry and ASCourt J.Org.Chem, 37, 939 (1
972)).

(Ii) a method of treating an enol of formula (III) (which compound is in equilibrium with the tautomeric formyl acetate) under acidic conditions, often in the presence of a dehydrating agent, with a thiol of formula R ² SH [ For example PR Bernstein, Tetrahedron Letter
s , 1015 (1979)].

(Iii) treating the beta-alkoxy acrylate of formula (IV) under acidic conditions with a thiol of formula R ² SH, or with a thiolate of formula R ² SM (M is a metal ion, eg sodium ion). How to handle.

(Iv) The beta-chloroacrylate of formula (V) has the formula: R ² SM (M is a metal ion, eg sodium ion)
With thiolate.

(V) A method of treating a beta-sulfonyloxy acrylate of the formula (VI) with a thiolate of the formula: R ² SM (M is a metal ion, eg sodium ion).

(Vi) A method of removing a molecule of the thiol of formula: R ² SH from a dithio-acetal of formula (VII) under acidic conditions.

The intermediate shown in Process Diagram I can be prepared by the process shown in Process Diagrams II and III. In process charts II and III,
W, X, Y, Z, R ¹ , R ¹⁴ and R ¹⁵ have the meanings given above,
M is a metal atom (eg lithium atom) or a metal atom + associated halogen atom (eg MgI, M
gBr or Mg (l), and L is a halogen atom (bromine, iodine or chlorine atom).

For example, the ketoester of formula (II) can be prepared by the following method. Each reaction is often conducted in a convenient solvent.

(I) metallated specie of formula (VIII)
s) is treated with an oxalate of the formula: R ¹ O ₂ C.CO ₂ R ¹ .
It is preferred to slowly add the solution of metal-binding species (VIII) to the solution of excess oxalate being stirred [eg LM Weinstock.RB Currie and AV Lovell, Synth.C.
ommu. , 11 , 943 (1981) and references therein]. M is M
The metal binding species (VIII) (Grignard reagent) which is gI, MgBr or MgCl can be prepared by standard methods from the corresponding halobenzene (XI) where L is I, Br or Cl respectively. Metal-bound species (VIII) where M is lithium can be prepared from the corresponding halobenzene (XI) by metal-halogen exchange with, for example, n-butyllithium using standard methods.
For certain substituents X, Y and Z, the direct lithiation of compound (IX) wherein the metal-binding species (VIII) where M is lithium uses a strong lithium base such as n-butyllithium or lithium diisopropylamide. (Lithiati
on) [eg HWGschwend and HR
Rodriguez, Organic Reactions , 26, 1 (1979)].

(Ii) in the presence of a catalytic or stoichiometric amount of an acid, in particular a Lewis acid, eg an alkyl oxalyl of the formula: R ¹ O ₂ C.COCl.
A method of performing Friedel-Crafts acylation of substituted benzene (IX) using chloride.

(Iii) A method of oxidizing a phenylacetate of formula (X), for example using selenium dioxide.

The beta-alkoxy acrylates of formula (IV) may be prepared from the enols of formula (III) under acidic or basic conditions by the following methods: (i) alcohols and acids of R ¹⁴ OH and optionally formula (R
¹⁴ O) A method using a dehydrating agent such as ₃ CH trialkyl orthoformate. The reaction solvent may be formed by alcohol or an inert solvent may be further used.

(Ii) Using a base (eg potassium carbonate or sodium hydride) and a species of general formula R ¹⁴ L in a suitable solvent.

The beta-chloro acrylate of formula (V) may be prepared from the enol of formula (III) using a chlorinating agent such as phosphorus pentachloride and often in a suitable solvent such as a chlorinated hydrocarbon.

The beta-sulfonyloxy acrylate of formula (VI) uses the sulfonyl chloride of formula: R ¹⁵ SO ₂ Cl, and
It may be prepared from the enol of formula (III), usually in the presence of a base such as triethylamine or pyridine, and usually in a suitable solvent.

An enol of formula (III) is prepared by treating a phenylacetate of formula (X) with a base (eg sodium hydride) and a formate ester of the general formula: HCO ₂ R ^{1 in} a suitable solvent followed by a mineral acid. Can be manufactured.

Halobenzenes of formula (XI), benzene of formula (IX) and phenylacetates of formula (X) may be prepared by standard methods described in the literature.

The compounds of the present invention are particularly effective as fungicides against the following diseases: -Pyricularia oryzae of rice; Rust of wheat ( Puccinia recondita , Puccinia strii)
formis and other rust), barley rust ( Puccinia ho)
rdei , Puccinia striiformis and other rusts) and other host plants such as coffee, pear, apples, peanuts, vegetables and ornamental rusts; barley and wheat powdery mildew ( Erysiphe gramihis ) and hops powdery mildew ( Sphaerotheca macularis), powdery mildew of cucurbits (e.g. Kiyuuri) (Sphaerotheca fuliginea), apple powdery mildew (Podosphaera leucotricha) and vine powdery mildew (Uncinula necator) various host plants other powdery mildew on such as; cereals Powdery mildew ( Helminthosporium spp and Pseudocercosporella he
rpotrichoides ); Peanut cutlet disease ( Cercospora a)
rachidicola and Cercosporidium personata ) and other hosts, such as sugar beet , banana, soybean and rice hanten ( Cercospora spp ); vegetables (eg cucumber), rape, apple, tomato and other host Alternaria spp; Kurohoshi (Venturia inaequalis) of apple and downy mildew of grape (downy m
ildew) ( Plasmopara viticola ).

Lettuce downy mildew ( Bremia lactucae ), soybean, tobacco,
Downy mildew of onions and other host plants ( Peronospora sp
p) and downy mildew of hop ( Pseudopernospora humuli )
And cucumber downy mildew ( Pseudoperonospora spp); potato and tomato blight ( Phytophthora infestanc)
e ); and other blight of vegetables, strawberries, avocados, koi, ornamental plants, tobacco, cocoa and other host plants ( Phytophthora spp.).

Some of the compounds according to the invention show a broad spectrum of activity against fungi in vitro.

These compounds are also found in various post-harvest diseases of fruits, such as orange curdew ( Penicillum digatatum and ita).
licum and Tricoderma viride ) and banana tanso disease ( Gloeosporium musarum ). Furthermore, some of the compounds of the present invention show activity as seed dressing agents.

The compounds of the invention are able to migrate locally in the leaves of plants and even phenotypically in plant tissues. Furthermore, the compounds of the invention are sufficiently volatile to be active in the form of steam against fungi on plants.

The compounds according to the invention are useful as industrial fungicides (in the agricultural sense); for example in protecting wood, leather, leather and especially paint coatings from the action of fungi.

The compounds of the present invention may exhibit useful insecticidal activity against a range of insect species and nematodes and may exhibit knockdown activity against flies and mosquitoes. Therefore, according to the present invention, there is further provided a method for controlling harmful insects or nematodes, which comprises applying the insecticide / nematicide compound of the general formula (I) to the pest or a place where the pest inhabits. It

Preferred compounds for use in the method of the invention are those in which one of W, X, Y and Z in general formula (I) is a substituted phenyl group such as a phenylethyl group.

A particularly preferred compound for use in this method is Compound No. 9 of Table I.

Similarly, certain compounds exhibit plant growth regulating activity and can therefore be used for this purpose at appropriate application rates. Therefore, according to the present invention, there is further provided a plant growth regulating method which comprises subjecting a plant to an effective amount of the compound of the general formula (I).

Therefore, the present invention includes not only the use of the above-mentioned compound mainly as a bactericide but also the use for the above-mentioned purpose (and the composition containing this compound).

While the compounds of the present invention may be used as such as a fungicide, it is more convenient to formulate a composition for use in such applications. Thus, according to the present invention there is provided a fungicide composition comprising a compound of the general formula (I) and optionally a carrier or diluent.

According to the present invention, there is further provided a method for controlling fungi of plants, which comprises applying the compound of the general formula (I) to plants or seeds of plants, or places where plants or seeds of plants live. To be done.

The compounds of the present invention may be applied in various ways; for example, these compounds may be formulated or not, directly on the leaves, seeds of the plant, or on the growing or planted plant. It can be applied to other media. The compounds can be applied by spraying or dusting or as a cream or paste formulation or in the form of steam or in the form of slow-acting granules. Application may be carried out on any part of the plant, such as the leaves, stems, branches or roots, or the soil around the roots or the seed or soil before sowing, usually paddy water or a hydroponic medium system. it can. Also, the compounds of the present invention can be injected into the plants or can be applied to the plants using electric spraying methods.

The term "plant" as used herein is intended to include seedlings, shrubs and trees. Further, the sterilization method according to the present invention includes preventive, protective and eradicative treatments.

The compounds according to the invention are preferably used in agricultural and horticultural form in the form of compositions. The type of composition used will vary depending on the particular intended purpose.

The composition comprises an active ingredient (a compound of the invention) and a solid diluent or carrier, such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, diatomite and porcelain clay. Can be in the form of a dusting powder or granules. Such granules may be preformed granules suitable for application to soil without further treatment. These granules can be prepared by impregnating a filler pellet with the active ingredient or pelletizing a mixture of the active ingredient and a powder filler. The composition for seed dressing may, for example, contain an agent which facilitates the adhesion of the composition to the seed (eg mineral oil); it may also be active using organic solvents such as N-methylpyrrolidone, propylene glycol or dimethylformamide. The ingredients may be formulated for seed dressing. The composition can also be in the form of a dispersible powder or granules that includes a wetting or dispersing agent to facilitate dispersion of the powder or granules in the liquid. Such powders or granules can additionally contain fillers and suspending agents.

The emulsifiable concentrate or emulsion is prepared by dissolving the active ingredient in an organic solvent which may optionally contain wetting or emulsifying agents,
It can then be prepared by adding the resulting mixture to water, which may also contain wetting or emulsifying agents. Suitable organic solvents are aromatic solvents such as alkylbenzene and alkylnaphthalene, ketones such as isophorone, cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichloroethane and benzyl alcohol, furfuryl alcohol, butanol and glycol ethers. It is alcohol.

Suspension concentrates of very poorly soluble solids can be prepared by ball or bees milling with a dispersant and then adding the suspending agent to prevent settling of the solid.

Nebulized compositions can also be in the form of an aerosol in which the formulation is held in a pressurized container in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane.

Also, the compound is a dry smoke mixture (Pyrotechnic mixt
It can also be mixed with nre) to give a composition suitable for generating smoke containing the compound in an enclosed space.

Alternatively, the compounds of the invention may be used in the form of microcapsules. The compound may also be a biodegradable polymeric formulation in order to provide slow and controlled release of the active ingredient.

To better suit different compositions for different intended uses by incorporating suitable additives, such as additives for improving spreadability, adhesion and rain resistance to the surface to be treated. You can

The compounds according to the invention can also be used as a mixture with fertilizers (for example fertilizers containing nitrogen, potassium or phosphorus). Compositions consisting only of fertilizer granules in which the compound is incorporated, for example by coating, are preferred. Such granules contain 25% by weight of active compound
It is suitable to contain in an amount up to. Therefore, according to the present invention, there is further provided a fertilizer composition containing a compound of the general formula (I).

Wettable powders, emulsifiable concentrates and suspension concentrates will usually contain surface-active agents, for example wetting agents, emulsifying agents or suspending agents. Such agents can be cationic, anionic or nonionic active agents.

Suitable cationic activators are quaternary ammonium compounds such as cetyltrimethylammonium bromide.

Suitable anionic activators include soaps, salts of aliphatic monoesters of sulfuric acid (eg sodium lauryl sulphate),
Salts of sulphonated aromatic compounds (for example sodium dodecylbenzene sulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate and mixtures of diisopropyl- and sodium salts of triisopropylnaphthalene sulphonic acid).

Suitable nonionic activators are condensation products of ethylene oxide with aliphatic alcohols such as oleyl alcohol or cetyl alcohol or with alkylphenols such as octylphenol, nonylphenol or octylcresol. Other nonionic activators are partial esters derived from long-chain fatty acids and hexitol anhydride, condensation products of such partial esters with ethylene oxide and lecithin. Suitable suspending agents are, for example, hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose) and swelling clays such as bentonite and attapulgite.

Compositions used in the form of aqueous dispersions or emulsions are usually supplied in the form of a concentrate containing a high proportion of active ingredient and diluted with water before use. Such concentrates are often capable of withstanding long-term storage and, when diluted with water after such long-term storage, are capable of forming an aqueous formulation which remains homogenous for a sufficient period to be applied with conventional spray equipment. is necessary. Such concentrates may conveniently contain up to 95% by weight, preferably 10-85% by weight, for example 25-60% by weight, of the active ingredient. When diluted for the preparation of an aqueous preparation, such a preparation may contain various amounts of active ingredients depending on its intended use, but generally an aqueous preparation containing 0.0005 (usually 0.01) to 10% by weight of the active ingredient is used. Can be used.

The compositions of the present invention may further contain other compounds having biological activity, such as compounds having similar or supplemental bactericidal or plant growth regulating activity, or compounds having herbicidal or insecticidal activity. .

Other fungicide compounds that may be present in the compositions of the invention are cereal (eg wheat) ear diseases such as Septoria, Gi.
It is a compound that can eradicate bberella and Helminthoporium , diseases that occur in seeds and soil, downy mildew and powdery mildew of grapes, and powdery mildews such as apples.
By including other fungicides, the composition may have a broader range of activity than the compound of general formula (I) alone. Examples of other fungicides that may be present in the compositions of the present invention include carbendazim, benomyl, thiophenate.
Methyl, thiabendazole, fuveridazole, etridazole, diclofluanid, simoxanil, oxadixyl, offlace, metalaxyl, furalaxyl, 4-
Chloro-N- (cyanoethoxymethyl) benzamide,
Benalaxyl, fuosetyl-aluminum, fenarimol, iprodione, procymidone, vinclozolin,
Penconazole, microbutanil, propamocarb, ziconazole, pyrazofuos, etirimol, zitalimfuos, tridemorph, trifluoroline, nuarimol, triazbutyl, guazatine, 1,1'-iminodi (octamethylene) diguanidine triacetate, butiobate, propiconazole, prochloraz, furtriafurol Nazole, i.e. 1- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -hexan-2-ol, (2 RS , 3 RS ) -2- (4
-Chlorophenyl) -3-cyclopropyl-1- (1H-
1,2,4-triazol-1-yl) -butan-2-ol, ( RS ) -1- (4-chlorophenyl) -4,4-dimethyl-3- (1H-1,2,4-triazole- 1-ylmethyl) pentan-3-ol, flusilazole, pyriphenox, mefon, triadimenol, diclobutrazol, heenpropimorph, huenpropidin, chlorozolinate, imazalil, huenfram, carboxin, oxycarboxin, metofloxam. , Dodemorph, BAS454, blasticidin S, kasugamycin, edifenfuos, kitadine P, cycloheximide, phthalide, probenazole, isoprothiolane, tricyclazole, pyroquillan, chlorobenzothizone, neoasodine, polyoxin D, validamycin A, mepronil, flutolanil, pencyclo , Diclomedine, phenazine oxide, nickel dimethyldithiocarbamate, teclophthalam, bitertanol, bupirimate,
Etaconazole, hydroxyisoxazole, streptomycin, ciprofram, viloxazole, quinomethionate, dimethylmol, 1- (2-cyano-2-
Methoxyiminoacetyl) -3-methylurea, phenapanil, tolclofuos-methyl, piroxifur, polyrum, maneb, mancozeb, captophor, chlorothalonil, anilazine, thiram, captan, phorpetet, zineb, propineb, sulfur, zinocap, dicron, chloroneb, vinapacryl, Nitrotal-isopropyl, todine, dithianon, fuentin hydroxide, fuentin acetate, technazen, quintozen, dichlorane,
Copper compounds such as copper oxychloride, copper sulfate and Bord-mixtures, organomercury compounds.

The compounds of general formula (I) may be mixed with soil, compost or other media for the protection of plants from disease caused by fungi occurring on soil, seeds, soil or leaves.

Suitable insecticides that may be incorporated into the compositions of the present invention include pirimicarb, dimethoate, demeton-s-methyl, formothione, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinone, fuenthione, phennitrothion, founto, chlorpyrihuos. , Isoxathion, propofus, monocrotophas, buprofezin, esroproxifene and cycloprothrin.

Plant growth regulators are weed growth or seedhead
Plants that inhibit the formation of plants and are undesirable (eg weeds)
It is a compound that selectively suppresses the growth of.

Examples of suitable plant growth regulators are gibberellins (eg G
A ₃ , GA ₄ or GA ₇ ), auxin (eg indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), cytokinin (eg kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acid (eg. 2.4-D
Or MCPA), substituted benzoic acid (eg triiodobenzoic acid), morphactin (eg chlorfluorecole), malein hydrazide, glyphosate, glyphosine, long-chain fatty alcohols or fatty acids, dikegrask,
Paclobutrazol, flurpyrimidol, mefluidide, substituted quaternary ammonium and phosphonium compounds (eg chlormequat, chlorphonium or mepicato chloride), etepon, carbetamide, 3,6-
Methyl dichloromethylanisate, daminozide, aslam, abscisic acid, isopyrimol, 1 (4-chlorophenyl) -4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitrile (eg bromoxynil) , Diphenzoquat, benzoylprop-ethyl, 3,6-dichloropicolinic acid, phenpentezole, enafenfide, trifpentanol and technazene.

Examples of the present invention are shown below.

In the examples, the "ether" prognosis means diethyl ether, the solution was dried over magnesium sulfate, and all experiments using water sensitive intermediates were conducted under a dry nitrogen atmosphere. I went below. Unless otherwise stated, chromatography was performed using silica gel as the stationary phase. Where infrared absorption spectra and NMR data are shown, these are the selected data; not all absorptions were done. The following abbreviations were used throughout the examples: Example 1 This example illustrates the preparation of ( E ) -methyl 2-phenyl-3- (methylthio) propenoate (Table I, Compound No. 1).

A solution of methyl phenylacetate (16.03g) in methyl formate (132ml) and anhydrous DMF (100ml) was added to a stirred suspension of sodium hydride (5.14g) in anhydrous DMF (200ml) 0-5. It was added dropwise at 40 ° C. for 40 minutes (boiling and foaming). The resulting mixture was stirred at about -5 ° C for 30 minutes and dried with anhydrous DMF (250 m
It was diluted with l) and then warmed and stirred at room temperature for 3 hours. Ice and sodium carbonate were added to the mixture, washed with ether (2 times), acidified with concentrated hydrochloric acid and then extracted with ether (4 times). The extract was washed with water (3 times), treated with magnesium sulfate and charcoal, passed and concentrated to give methyl 3-hydroxy-2-phenylpropenoate (13.56g, 71%) as a solid. (Mp33.5-35.5
C), which was used in the next step without further purification.

Phosphorus pentachloride (4.03 g) was added in small portions to a stirred solution of methyl 3-hydroxy-2-phenylpropenoate (2.65 g) in dichloromethane (40 ml), which was cooled in a water bath ( boiling). After 45 minutes, remove the cooling bath,
The resulting mixture was stirred at room temperature for 75 minutes then poured into water. The organic layer was separated and the aqueous phase was further extracted with dichloromethane. The combined organic layers were washed with aqueous potassium carbonate solution (2 times), then with water (3 times), dried and concentrated to give a pale yellow liquid (3.09 g). This crude product was combined with a similar crude product (227 mg) obtained from a small scale preliminary pilot test and then chromatographed using ether containing 12% ether ( E )-
Methyl 3-chloro-2-phenylpropenoate (1.
83 g, yield 58%) was obtained as a colorless fluid liquid. ¹ H NMR
(CDCl ₃ ) δ: 3.79 (3H, s), 7.61 (1H, s) ppm.

Ice- ( E ) in DMF (5 ml), cooled in a water bath-
Methyl 3-chloro-2-phenylpropenoate (23
To a stirred solution of 6 mg) was added a solution of sodium methanethiolate (96 mg) in water (2 ml). After 5 minutes the cooling bath was removed and after 1.5 hours at room temperature the mixture was poured into water and extracted with ether. The extract was washed with aqueous potassium carbonate solution (twice) and then water (three times), dried and concentrated to give the title compound (224 mg, yield 86%) as a colorless oil (purity 96 by GC). %; Contains 2% of the corresponding (Z) -isomer). ¹ H NMR (CDCl ₃ ) δ: 2.42
(3H, s), 3.76 (3H, s), 7.82 (1H, s) ppm. The product crystallized on standing to give a white solid (mp49-52
C). Recrystallization from gasoline (40-60 ° C) gave colorless flakes (mp 54-55 ° C). Found: C, 63.3; H, 5.9%;
Theoretical value for C ₁₁ H ₁₂ O ₂ S: C, 63.44, H, 5.81%.

Example 2 This example describes ( E ) -methyl 2- (2-phenoxyphenyl) -3- (methylthio) propenoate (Table II,
The production of compound No. 1) is exemplified.

Diphenyl ether (34.) in anhydrous ether (300 ml).
N) to 0 g) of the stirred solution and cooled to about 0 ° C.
-Butyllithium (77 ml of 2.6M solution in hexane) was added dropwise over 30 minutes. The resulting orange solution was stirred at room temperature for 3 hours, allowed to stand overnight and then dried slightly below 10 ° C in anhydrous THF (2
To a stirred solution of dimethyl oxalate (47.0 g) in 00 ml) was added dropwise over 1.5 hours. The resulting solution was left overnight, poured into water and extracted with ether. The extract was washed with water, dried and concentrated under reduced pressure to give a brown oil (58.57g). A portion of this oil (12.20 g) was purified by column chromatography using gasoline containing 20% ether as eluent to give methyl o-phenoxybenzoyl formate (5.87 g, 55% yield). Was obtained as a pale yellow oil.

To a stirred solution of (methylthiomethyl) -toluphenylphenylnium chloride (11.26g) in anhydrous ether (150ml) was added potassium t -butoxide (3.02g) in one portion. Immediately a bright yellow color began to develop. After 40 minutes, a solution of methyl o- phenoxybenzoyl formate (4.06g) in anhydrous ether (20ml) was added rapidly at which time the color had disappeared. The reaction mixture was diluted with water for a further 3 hours and then extracted with ether. The extract was treated with magnesium sulfate and charcoal, passed, concentrated under reduced pressure and then rapidly passed through a short column of silica gel with ether to remove triphenylphosphine oxide to give a pale yellow solid (4.56). g) was obtained. This solid was triturated with gasoline containing a small amount of ether, and the obtained solid was recrystallized from dichloromethane and gasoline to give the title compound (1.01 g) as a pure white solid (mp96-
97.5 ° C.). An analytical sample recrystallized from a mixture of ether and gasoline had an mp of 98-98.5 ° C.
Infrared absorption spectrum (Nujiol): 1705,1569,1234c
m ^-1 . ¹ H NMR (CDCl ₃ ): δ 2.40 (3H, s), 3.62 (3H, s),
7.77 (1H, S) ppm. Found: C, 67.9; H, 5.3%; C ₁₇ H ₁₆ O ₃ S
Theoretical value for: C, 67.98; H, 5.37%. Methyl o -phenoxybenzoyl was obtained by subjecting the combined mother liquors from the above trituration and recrystallization operations to chromatography using an eluent containing 15% ether in gasoline. An additional amount of formate (1.46 g) and the title compound (0.76 g after recrystallization) was obtained. The yield of the title compound based on the recovered starting material was 48%.

Note: GC / MS for crude product from Wittig reaction above.
From the results of analysis using the title compound ( Z )
-Isomeres also exist, but were found to be very small. The ( E / Z ) -selectivity of the reaction was about 92: 8. Other similar Wittig reactions are often less selective, ( Z )
The isomer is isolated. For example, the reaction using methyl benzoyl formate gives compounds 1 and 2 of Table I in a ratio of about 2: 1 respectively.

Example 3 This example illustrates the preparation of ( E ) -methyl 2-([2- (2-furyl) ethyl] phenyl) -3- (methylthio) propenoate (Table I, Compound No. 9).

N-methyl 2-methylbenzoate in chloroform
-Bromsuccinimide followed by treatment with triphenylphosphine in toluene gave (o-methoxycarbonylbenzyl) triphenylphosphonium bromide as a white solid (mp 230-234 ° C). ¹ H NMR
(D ₆ -DMSO) δ: 3.36 (3H, s), 5.47 (2H, br dJ 17Hz) pp
m.

To a stirred solution of (O-methoxycarbonylbenzyl) -triphenylphosphonium bromide (45g) in anhydrous dichloromethane (about 760ml) was added 1,8-diazolobicyclo [5.4.0] undec-7-ene (10.72g). ) Was added to give an orange-red reaction mixture. After 20 minutes, a solution of furfural (5.56 g) in dichloromethane (about 40 ml) was added, the color disappearing. The resulting reaction mixture was stirred at room temperature for 1.5 hours then diluted with water. The aqueous layer and the organic layer were separated, and the latter was washed with aqueous sodium hydrogen carbonate
Times), brine and water, dried and concentrated to give a yellow solid (46.77g). A solution of this solid in a mixture of ether and gasoline was eluted from a short column of silica gel using a mixture of ether and gasoline to remove triphenylphosphine oxide and excess starting phosphonium salt. The material obtained was chromatographed using gasoline containing 15% ether as eluent to give methyl 2- [2
-(2-Furyl) ethenyl] benzoate (12.87 g, 97% yield) was obtained as a yellow oil.

A portion of this ester (11.45 g) was dissolved in ethyl acetate (70 ml) containing 10 w / w% palladium on carbon (1.2 g) and the solution was hydrogenated under a hydrogen pressure of 2 atm. The catalyst was removed by filtration, and the solution was concentrated to give methyl 2-
[2- (furyl) -ethyl] benzoate (11.18 g, yield 96%) was obtained as a colorless liquid. ¹ H NMR (CDCl ₃ ): δ
2.91-2.97 (2H, m), 3.23-3.39 (2H, m), 3.89 (3H, s, 5.9
6 (1H, m), 6.25 (1H, m), 7.15-7.42 (4H, m), 7.89 (1H,
m) ppm.

Methyl 2- [2- (2-furyl) ethyl] benzoate was treated with methyl 2- [2- (2-furyl) by the following four steps.
Ethyl] phenyl acetate: (a) reduction of benzoate to benzyl alcohol with lithium aluminum aluminum in ether; (b) benzyl alcohol to the corresponding benzyl chloride using thionyl chloride and triethylamine in dichloromethane. (C) converting benzyl chloride to the corresponding phenylacetic acid by forming a Grignard reagent in ether and then treating it with carbon dioxide; and (d) phenylacetic acid in DMF. The process of esterification using potassium carbonate and dimethyl sulfate.

Methyl 2- [2- (2-furyl) ethyl] phenyl
Acetate is an oil: ¹ H NMR (CDCl ₃ , 60 MHz);
δ2.97 (4H, br.s), 3.68 (5H, br.s); ppm.

A solution of methyl 2- [2- (2-furyl) ethyl] phenylacetate (2.27g) in methyl formate (5.7ml) and anhydrous DMF (about 10ml) was cooled to about 0 ° C in an ice bath, Sodium hydride (0.938) in anhydrous DMF (about 40 ml)
g) was added dropwise to the stirred suspension (boiling). After the addition, the reaction mixture was warmed to room temperature and then stirred for 3.5 hours. Water was added to the reaction mixture, which was then acidified with hydrochloric acid and then extracted with ether. The extract was extracted with water and concentrated to give a pale yellow gum (1.62g). To a stirred solution of a portion (0.65 g) of this gum in anhydrous dichloromethane (10 ml) was added triethylamine (0.29 ml) followed 5 minutes later by methanesulfonyl chloride (0.21 ml). After 1 hour, dry DMF (10 ml) was added to the reaction mixture.
And sodium methanethiolate (0.202 g) were added and the mixture was stirred for 4 hours. The mixture was diluted with water and extracted with ether. The extract was washed with water, dried, concentrated and chromatographed to give the title compound (0.303 g, 27% yield from phenylacetate) as a gum. ¹ H NMR (CDCl ₃ ): δ2.72-2.90 (4H, m), 3.04 (3H,
s), 3.78 (3H, s), 5.95 (1H, d), 6.26 (1H, m), 7.08 (1
H, d), 7.2-7.35 (4H, m), 7.99 (1H, s) ppm.

Example 4 This example is a preparation of ( E ) -methyl 2- (2- [2- (2- (4-fluorophenyl) ethyl] phenyl) -3- (methylthio) propenoate (Table I, Compound No. 96). Is illustrated.

By a method similar to that described in Example 3 for the production of methyl 2- [2- (2-furyl) ethyl] phenylacetate, 4-fluorobenzaldehyde and 10-methoxycarbonylbenzyl) triphenylphosphonium bromide to methyl 2- (2- [4-Fluorophenyl] ethyl) phenyl acetate was prepared. In this case, the benzyl chloride was treated with potassium cyanide in DMSO and the resulting phenylacetonitrile was then treated with methanol in sulfuric acid in methanol.
It was converted to phenylacetate by lysis.

A solution of methyl 2- (2- [4-fluorophenyl] ethyl) phenylacetate (2.83 g) and methyl formate (12.8 ml) in anhydrous DMF (20 ml) was cooled in an ice bath. DMF (30 ml) was added dropwise to a stirred solution of sodium hydride (0.50 g) over 20 minutes. Boiling and foaming occurred. When it subsided, the reaction mixture was allowed to warm to room temperature and then stirred for 3.5 hours. The reaction mixture was diluted with water, acidified with concentrated hydrochloric acid and then extracted with ether. The extract was washed with water, dried and concentrated. A solution of the thus obtained viscous yellow oil (3.34 g) in DMF (30 ml) was treated successively with potassium carbonate (3.05 g) and dimethyl sulfate (1.54 g). After 2 hours, the reaction mixture was poured into water and extracted with ether. The extracts are washed with water, dried, concentrated and then chromatographed using gasoline containing 30% ether ( E ) -methyl 2- (2- [2- [2-
(4-Fluorophenyl) ethyl] phenyl-3-methoxypropenoate (2.64 g, 81% yield) as a colorless solid (m.
p.41.5-42.5 ° C). ¹ H NMR (CDCl ₃ ); δ2.76
(4H, br s), 3.70 (3H, s), 3.82 (3H, s), 7.58 (1H, s)
ppm.

Methane thiol (2 ml) with acetone dry ice
Concentrated in trap. This was allowed to warm to room temperature and in a flask fitted with a dry ice condenser, ( E ) -methyl 2- (2- [2- (2-fluorophenyl) ethyl] phenyl) -3-methoxypropenoate ( 1.22 g) and anhydrous dichloromethane (20 ml) containing a catalytic amount of 4-toluenesulfonic acid were bubbled into a stirred solution. The resulting mixture was stirred at room temperature for 2
It was stirred for an hour and then heated under reflux of dichloromethane for 6 hours and then allowed to cool. After addition of aqueous sodium hydrogen carbonate solution, the organic layer is separated, washed twice with water, dried, concentrated and chromatographed using 30% ether in gasoline as eluent to give methyl 2- (2 -[2- (4-Fluorophenyl) ethyl]
Phenyl) -3,3-di- (methylthio) propanoate (423 mg, yield 34% based on starting materials) was obtained as a colorless glass. ¹ H NMR (CDCl ₃ ): δ1.98 (3H, s), 2,21
(3H, s), 2.85-3.05 (4H, m), 3.72 (3H, s), 4.24 (1H, d
J 13Hz), 4.41 (1H, d J 13Hz) ppm.

The recovered ( E ) -methyl 2- (2- [2- (2-fluorophenyl) ethyl] phenyl) -3-methoxypropenoate (191 mg) and traces of the title compound were also isolated.

Methyl 2- (2- [2- (4
-Fluorophenyl) ethyl] phenyl) -3,3-di (methylthio) propanoate (350 mg) in a stirred and cooled solution to -40 ° C, titanium tetrachloride (0.
12 ml) and after 10 minutes triethylamine (0.16 ml) was added sequentially. The resulting mixture was stirred at −40 ° C. for 20 minutes, allowed to warm to room temperature, washed twice with water, dried and concentrated to give a pale yellow glass (292 mg). From the results of GC analysis, it was confirmed that relatively volatile impurities were present, and these impurities were removed by heating at 140 ° C and 0.01 mmHg. The residue was chromatographed using gasoline containing 15% ether to give the title compound (239 mg, 95% pure by GC, 73% yield) as a viscous oil. ¹ H NMR (CDCl ₃ ): δ 2.40 (3H, s), 2.7-2.9
(4H, m), 3.72 (3H, s), 7.90 (1H, s) ppm.

The following are examples of compositions suitable for agricultural and horticultural purposes that may be formulated from the compounds of the present invention. In the examples, temperature is in degrees Celsius (° C) and% is by weight.

Example 5 The following ingredients were mixed and the mixture was stirred until all ingredients were dissolved to prepare an emulsifying stock solution: Compound of Example 2 10% Benzyl alcohol 30% Calcium dodecylbenzene sulfonate 5% Nonylphenol ethoxylate (Ethylene oxide 13
Mol) 10% Alkylbenzene 45% Example 6 After dissolving the active ingredient in methylene dichloride, the resulting solution was sprayed onto attapulgite clay granules. The solvent was then evaporated to obtain a granular composition: compound of Example 2 5% attapulgite granules 95% Example 7 The following 3 ingredients were crushed and mixed to prepare a seed dressing agent: Example 2 Compound 50% Mineral oil 2% Clay 48% Example 8 A dusting powder was prepared by grinding and mixing the active ingredient and talc: Compound of Example 2 5% Talc 95% Example 9 The following ingredients were ball milled. The milled mixture was then suspended in water to prepare a suspension concentrate of the drug, which is a solid with low solubility.

Compound of Example 2 40% Sodium lignosulfonate 10% Bentonite clay 1% Water 49% This formulation can be used as a spray liquor by dilution with water or by direct application to the seeds.

Example 10 A dispersible powder formulation was prepared by mixing the following ingredients and milling the mixture until all ingredients were thoroughly mixed: Compound of Example 2 25% Sodium lauryl sulfate 2% Sodium lignosulfonate 5 % Silica 25% Clay 43% Example 11 The compounds of the present invention were tested against diseases caused by various fungi parasitic on leaf of plants. The test method used is as follows.

The test plants were grown in a small pot with a diameter of 4 cm in Jiyoung Innes potting compost (No. 1 or No. 2). The test compounds were bead kneaded with an aqueous solution of Dispersol T or formulated as a solution in acetone or acetone / ethanol (which was diluted to the required concentration immediately before use). For leaf diseases, the formulation (active ingredient 100pp
m) was sprayed onto the leaves and applied to the roots of the plants via soil.
The spray liquor was applied to maximize retention and the root drench liquid was applied to a final concentration equal to about 40 ppm active ingredient per dry soil. Tween 20 was added to a final concentration of 0.05% when the spray was applied to the grain.

For most tests, the test compound is the soil (root) and leaves (by spraying) 1-2 days before inoculating the plant with the pathogen.
Applied to. In the test for Erythiphe graminis , the plants were inoculated 24 hours before treatment. Leaf pathogens were sprayed onto the leaves of the test plants as a spore suspension. After inoculation, the plants were transferred to an appropriate environment to infect and then cultured until the degree of disease was evaluated. The period from inoculation to evaluation was 4 to 14 days depending on the type of disease and environment.

Disease control was recorded according to the following grades: 4 = no disease 3 = minor -5% compared to disease produced in untreated plants 2 = equivalent to 6-25% of disease produced in untreated plants 1 = not Equivalent to 26-59% of the disease caused on the treated plants 0 = Equivalent to 60-100% of the disease caused on the untreated plants Table V shows the results obtained.

Example 12 This example demonstrates the insecticidal activity of the compounds in Table I.

The activity of this compound was measured using various insects, mites and nematodes. The test compound was used in the form of a liquid preparation containing 100 to 500 ppm (weight) of the compound. This formulation was prepared by dissolving the test compound in acetone and obtaining a liquid formulation containing the test compound at the desired concentration until 0.1% by weight of the wetting agent "SYNPERONIC" NX ["Symperonik"(" SYNPERONIC ") is a registered trademark] and diluted with water.

The test methods employed for each pest are basically the same, usually a large number of pests are placed on a medium that is the host plant or food that feeds the pests and then one or both of the pests and the medium is formulated. It went by processing. Then, the mortality of the harmful insects was evaluated usually 1 to 7 days after the treatment.

The test results for each of the test compounds are shown in Table VII. The application rate of each compound expressed in ppm is shown in the second column of the table. Insecticidal activity was expressed in the grades of 9, 5 and 0: 9 killed 80-100% (for Meloidogyne incognita , the root knot reduction rate compared to untreated plants).
duction) is 70-100%), 5 is 50-79% mortality (50% -69% root knot reduction rate for Meloidogyne incognita ), 0 is mortality (Meloidogyne incognita) Indicates that the root note reduction rate) is less than 50%.

The pests tested are shown symbolically in Table VII and the pest type, support medium or food and test type and duration are shown in Table VI.

Compound No.9 of Table I Musca M. domestica (Musca Dom
The knockdown activity for estica ) ( housefly ) is shown below.

A sample of compound 9 was diluted with 2 ml of acetone and then made into a solution having a concentration of 2000 ppm with an aqueous 0.1% synperonic solution.
This solution (1 ml) was then sprayed directly onto 20 male and female house flies housed in a drinking cup. Immediately after spraying, the cup was tumbled and dried. After 15 minutes, when the cup was upright, knockdown was evaluated. Then, the house fly was given a 10% sucrose solution on raw cotton and kept in a storage room conditioned at 25 ° C and relative humidity of 65 ° C for 48 hours, and then the mortality was examined.

Under these conditions, compound 9 had a knockdown rate of 88% and 15
It showed a mortality rate of%.

Example 13 This example describes compounds 1, 2, 9, 10, and 96 of Table I and
2 illustrates the plant growth regulating properties of Compound 1 in Table II.

Using these compounds, the whole plant part selection test (Whole Plan) for plant growth activity against 6 types of plants
t Screen). The plant types used in this study and the leaf stages when sprayed with the drug are shown in Table VIII.

Each drug has a track player and SS 8
4000 ppm using a 004 E (Teejet) nozzle (4 kg / hectare at a spray volume of 1000 l / hectare)
I gave it in. However, for tomatoes, additional tests were conducted at 2000 and 500 ppm.

After spraying, the plants were grown in a greenhouse at a daytime temperature of 25 ° C / nighttime temperature of 22 ° C. Exceptions are cereal wheat and barley, daytime temperatures 13
Growing at -16 ℃ / night temperature 11-13 ℃. 16 hours (minimum 14
Time) was supplemented with light when necessary to obtain the average irradiation time.

After left in the greenhouse for 2-6 weeks depending on the time of year of the plants, the plants were visually inspected for morphological characteristics relative to untreated control plants. Test results are IX
Shown in the table.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 323/58 323/65 C07D 213/55 307/91 319/24 333/24 339/08 (72 ) Inventor Jiyeon Martin Crow United Kingdom. Berkshire. Black nails. Jiarotsutsu Hill Research Station (Street number and others not shown) (72) Inventor Paul Defrain England. Berkshire. Black nails. Jarots Hill Research Station (Street number and others not shown) (72) Inventor Christopher Lichyard Iris Gottoffrey United Kingdom. Berkshire. Black nails. Jarots Hill Research Station (Street number and others not shown) (72) Inventor David W. Jozef Tapolkusey England. Berkshire. Black nails. Jarots Hill Research Station (No. and other not shown) (72) Inventor Thomas Yuzien Wiggins UK. Berkshire. Black nails. Jiarotsutsu Hill Research Station (No other address displayed)

Claims (7)

[Claims] 1. General formula (I): (In the formula, R ¹ and R ² are the same or different,
And represents an optionally substituted alkyl group; W,
X, Y and Z are the same or different and are hydrogen, halogen, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkyl An alkyl group, an optionally substituted aralkyl group, an optionally substituted aryloxyalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group,
An optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted arylazo group,
Optionally substituted heteroarylalkyl group, optionally substituted heteroaryloxy group, an optionally substituted acylamino group, a nitro group, a cyano ^{group, -OR 3, -SR 3, -CO} 2 R 4, - CONR ⁵ R ⁶ , -COR ⁷ , -CR
^{8 = NR 9, -N = CR} 10 R 11, or represents -SOR ¹² or -SO ₂ R ^13, or, W in adjacent positions on the phenyl ring, X,
Any two of Y and Z are optionally joined to form an optionally substituted fused ring which is an aromatic ring or an aliphatic ring and which optionally contains one or more heteroatoms. R ³ is an optionally substituted alkyl group or a cycloalkyl group optionally containing a heteroatom in the cycloalkyl ring, an optionally substituted alkenyl group, an optionally substituted aryl group, optionally Represents a substituted aralkyl group, an optionally substituted acyl group or an optionally substituted heteroaryl group; are R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ the same? Or a different and hydrogen or an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkylalkyl group, an optionally substituted Represents a substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group; and R ⁹ , R
¹² and R ¹³ represent an optionally substituted aryl group or a substituted heteroaryl group), and the stereoisomers thereof. 2. General formula (Ia): Wherein W, X, Y and Z are the same or different and are substituted by hydrogen, halogen, optionally a hydroxyl group or a C _1-4 alkoxycarbonyl group
C _1-4 alkyl group, trifluoromethyl group, phenyl (C
_1-4 ) Alkyl groups, per se, optionally substituted or aromatic or heteroaromatic groups, in which the terminal carbon atom of the alkenyl group forms part of a 5- or 6-membered cycloalkyl group An optionally substituted C _2-4 alkenyl group, an optionally substituted C _2-4 alkynyl group,
Optionally substituted aryl group, aryl group or C _1-4
An amino group substituted by an alkyl group, optionally substituted arylazo group, optionally substituted acylamino group, a nitro group, -SR ³ or -OR ³ (wherein the alkyl group optionally substituted with R ³ is An optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aralkyl group or an acyl group), -SOR ¹² or -SO ₂ R ¹³ (wherein R ¹² and R ¹³ are , An aryl group, or —CO ₂ R ⁴ , wherein R ⁴ is an optionally substituted alkyl group, an aryl group, a C _3-6 cycloalkyl group, a C _3-6 cycloalkyl (C _1-4 ) alkyl group or An aryl (C _1-4 ) alkyl group) or —COR ⁷ (wherein R ⁷ represents an optionally substituted alkyl group or an optionally substituted aryl group), or on a phenyl ring W in adjacent position X, any two of Y and Z is a compound and its stereoisomers represented by bonded to form a condensed ring], acrylic acid derivative as set forth in claim 1, wherein the appended claims. 3. The general formula (Ib): [Wherein R is hydrogen, a C _1-4 alkylthio group, a C _1-4 alkyl group optionally substituted by a phenylthio group or a phenyl group, a C _3-6 cycloalkyl group, a tetrahydropyranyl group, C _2-4 Alkenyl group, phenyl group or halogen, hydroxyl group, C _1-4 alkyl group, C _1-4 alkoxy group, trifluoromethoxy group, phenoxy group, nitro group, amino group, aryl (C _1-4 ) alkyl group, phenyl group Group, carboxyl group, carboxylic acid ester group, cyano group, C _1-4 alkylcarbonylamino group or phenyl group, naphthyl group, pyridinyl group or pyrimidinyl group (pyridinyl group) substituted by one or more of methylenedioxy group and optionally substituted by halogen pyrimidinyl moiety, trifluoromethyl group, nitro group, C _1-4 alkyl, C _1-4 alkoxy group, Torufuruorumeto Represents a sheet which is substituted by a group or amino group), Y and Z are those or are the same, and hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy groups, C _1-4 alkylthio group, tolufluoromethyl group, nitro group or N , N -di (C _1-4 ) -alkylamino group, or Y and Z taken together form a methylenedioxy group. The acrylic acid derivative according to claim 1, which is a compound represented by the formula: 4. General formula (Ic): (In the formula, Y and Z have the same meanings as described in claim 3, provided that R is a thienyl group,
The acrylic acid derivative according to claim 1, which is a compound represented by a furyl group or a pyrrolyl group). 5. General formula (Id): The acrylic acid derivative according to claim 1, which is a compound represented by the formula (wherein Y and Z have the same meanings as those described in claim 4). 6. (i) General formula (II): The alpha-ketoester represented by the general formula: Ph
₃ P ⁺ - ^- phosphorane or represented by the general formula CHSR ^2: Me ₃ SiC
Or treated with a lithio species represented by H (Li) SR ² or (ii) general formula (III): Is treated with thiol R ² SH under acidic conditions or (iii) the general formula (IV): Is treated with thiol R ² SH under acidic conditions or thiolate
R ² SM or (iv) General formula (V): A beta-chloro acrylate of formula (v) is treated with thiolate R ² SM or (v) general formula (VI): Or treating the beta-sulfonyloxy acrylate represented by thiolate R ² SM or (vi) the general formula (VII): Removal of the thiol R ² SH molecule from the dithio-acetal represented by (wherein W, X, Y, Z, R ¹ and R ² have the meanings described below, and Ph is a phenyl group. , Me is a methyl group, R ¹⁴ is an alkyl group, R ¹⁵ is an alkyl group or an optionally substituted aryl group, and M is a metal ion), the general formula (I): (In the formula, R ¹ and R ² are the same or different,
And represents an optionally substituted alkyl group; W,
X, Y and Z are the same or different and are hydrogen, halogen, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkyl An alkyl group, an optionally substituted aralkyl group, an optionally substituted aryloxyalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group,
An optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted arylazo group,
Optionally substituted heteroarylalkyl group, optionally substituted heteroaryloxy group, an optionally substituted acylamino group, a nitro group, a cyano ^{group, -OR 3, -SR 3, -CO} 2 R 4, - CONR ⁵ R ⁶ , -COR ⁷ , -CR
^{8 = NR 9, -N = CR} 10 R 11, or represents -SOR ¹² or -SO ₂ R ^13, or, W in adjacent positions on the phenyl ring, X,
Any two of Y and Z are optionally joined to form an optionally substituted fused ring which is an aromatic ring or an aliphatic ring and which optionally contains one or more heteroatoms. R ³ is an optionally substituted alkyl group or a cycloalkyl group optionally containing a heteroatom in the cycloalkyl ring, an optionally substituted alkenyl group, an optionally substituted aryl group, optionally Represents a substituted aralkyl group, an optionally substituted acyl group or an optionally substituted heteroaryl group; are R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ the same? Or a different and hydrogen or an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkylalkyl group, an optionally substituted Represents a substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group; and R ⁹ , R
¹² and R ^{13 each} represent an optionally substituted aryl group or a substituted heteroaryl group), and a method for producing a stereoisomer thereof. 7. General formula (I): (In the formula, R ¹ and R ² are the same or different,
And represents an optionally substituted alkyl group; W,
X, Y and Z are the same or different and are hydrogen, halogen, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkyl An alkyl group, an optionally substituted aralkyl group, an optionally substituted aryloxyalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group,
An optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted arylazo group,
Optionally substituted heteroarylalkyl group, optionally substituted heteroaryloxy group, an optionally substituted acylamino group, a nitro group, a cyano ^{group, -OR 3, -SR 3, -CO} 2 R 4, - CONR ⁵ R ⁶ , -COR ⁷ , -CR
^{8 = NR 9, -N = CR} 10 R 11, or represents -SOR ¹² or -SO ₂ R ^13, or, W in adjacent positions on the phenyl ring, X,
Any two of Y and Z are optionally joined to form an optionally substituted fused ring which is an aromatic ring or an aliphatic ring and which optionally contains one or more heteroatoms. R ³ is an optionally substituted alkyl group or a cycloalkyl group optionally containing a heteroatom in the cycloalkyl ring, an optionally substituted alkenyl group, an optionally substituted aryl group, optionally Represents a substituted aralkyl group, an optionally substituted acyl group or an optionally substituted heteroaryl group; are R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ the same? Or a different and hydrogen or an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkylalkyl group, an optionally substituted Represents a substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group; and R ⁹ , R
¹² and R ^{13 each} represent an optionally substituted aryl group or a substituted heteroaryl group), which is a fungicide, insecticide or plant growth regulator composition comprising as an active ingredient an acrylic acid derivative and its stereoisomer.